KR20130008630A - High solids epoxy coating composition - Google Patents

Abstract

The present invention relates to a coating composition comprising a reaction product of tetra-alkoxyorthosilicate or its partially condensed oligomer and an epoxy resin containing a hydroxyl group, wherein the coating composition has a solids content of at least 70% by volume and / or 250 has a volatile organic content (VOC) of less than or equal to g / l.
Such coating compositions provide fast-curing and extended pot-life at ambient and below ambient temperatures.

Description

High solids epoxy coating composition {HIGH SOLIDS EPOXY COATING COMPOSITION}

The present invention relates to a coating composition comprising a silicate-modified epoxy resin.

In the present specification, the term "silicate" means a compound in which a silicon atom is not bonded to a carbon atom but is bonded only to an oxygen atom.

Silicate-modified epoxy resins are known from EP 1 114 834, and EP 1 114 834 is an alkoxy obtainable by dealcoholisation condensation reaction of a bisphenol epoxy resin, ie an aromatic epoxy resin, with a hydrolyzable alkoxysilane. A composition is disclosed, comprising a silicon-modified epoxy resin. Since this composition contains a high level of solvent, the solids content is typically low, up to 60% by volume. In addition, the composition is typically cured at high temperatures of 135-175 ° C.

In recent years, there has been a growing concern about the release of volatile solvents into the atmosphere, resulting in the need to reduce the volatile organic solvent content of coating compositions. Coating compositions to be applied by sprays, rollers or brushes, in particular coating compositions to be cured rapidly after application at ambient temperature, for example coatings for large structures such as ships, bridges, buildings, industrial facilities, and oil rigs Since the composition requires a relatively low viscosity of less than 20 poise, it is not easy to reduce the volatile organic solvent content of the coating compositions.

The coating composition generally needs to contain a polymer that imparts film-forming properties, but all polymers used must have sufficient molecular weight, especially after coloring, to provide the required low viscosity. However, low viscosity polymers often require a long curing time to obtain satisfactory mechanical properties, especially when cured at low temperatures.

Surprisingly, it has been found that silicate-modified epoxy resins can be used to prepare high solids content coating compositions having fast curing properties at or below ambient temperature.

The present invention relates to a coating composition comprising a reaction product of tetra-alkoxyorthosilicate or its partially condensed oligomer with an epoxy resin containing a hydroxyl group, wherein the coating composition has a solids content of at least 70% by volume and / or 250 has a volatile organic content (VOC) that does not exceed g / l.

The coating composition essentially comprises a reaction product, not a mixture of (partially hydrolyzed) tetra-alkoxyorthosilicate and an epoxy resin. The reaction product is obtained by reacting (partially hydrolyzed) tetra-alkoxyorthosilicate with an epoxy resin in the presence of an elevated temperature and catalyst as described in more detail below.

Since the reaction product of the (partially condensed) tetra-alkoxyorthosilicate with an epoxy resin (hereinafter referred to as "silicate-modified epoxy resin") has a very low viscosity, no additional solvent is required. Moreover, the coating composition according to the invention has an extended pot life.

As used herein, the terms "high solids content" and "high solids content" refer to at least 70 vol%, more preferably at least 80 vol%, and most preferably 85 vol, based on the total weight of the coating composition. It means a solid content of more than%. The maximum solids content is generally 95 vol% or less. Solids content of the composition can be measured according to ASTM standard D 5201-01.

The volatile organic content (VOC) of the coating composition preferably does not exceed 250 g / l, most preferably less than 100 g / l solvent per liter of the composition. VOC values can be measured by EPA reference method 24 in relation to ASTM standard D 3960-02.

The above values refer to the values of the complete coating composition. Thus, where the coating composition is in the form of a two-pack composition, the above values refer to the solids content and VOC in the composition after mixing the two packs.

Tetra-alkoxyorthosilicates and their partially condensed oligomers, which can be used to prepare silicate-modified epoxy resins, are represented by the following formulae.

RO-[-Si (OR) ₂ -O-] _n -R

In the above formula, each R is independently selected from alkyl groups and aryl groups having up to 6 carbon atoms, and -Si (OR) ₃ groups, n is 1 to 20.

In a preferred embodiment, R is selected from methyl, ethyl, propyl, isopropyl and butyl groups, more preferably R is an ethyl group.

Examples of suitable tetra-alkoxyorthosilicates include tetra-methoxyorthosilicate, tetra-ethoxyorthosilicate, tetra-propoxyorthosilicate, tetra-isopropoxyorthosilicate, tetra-butoxyorthosilicate and partially polymerized thereof Or oligomerized forms. Most preferred tetra-alkoxyorthosilicates are partially oligomerized tetra-ethoxyorthosilicates, such as the commercially available tetra-ethoxyorthosilicates TES40 (eg Wacker) and Dynasil 40 (eg Degussa).

The hydroxyl group containing epoxy resin that can be used in the present invention may be an aromatic or aliphatic epoxy resin. Preferably, the epoxy resin is an aliphatic epoxy resin. More preferably, mixtures of one or more aliphatic and one or more aromatic epoxy resins with hydroxy groups are used. The mixture of silicate-modified aliphatic epoxy resins, silicate-modified, one or more aliphatic and one or more aromatic epoxy resins has a lower viscosity compared to silicate-modified aromatic epoxy resins. Thus, silicate-modified aliphatic epoxy resins, optionally in combination with one or more silicate-modified aromatic epoxy resins, have lower viscosity and hence higher solids content and lower VOC compared to silicate-modified aromatic epoxy resins. Having a coating composition.

Accordingly, the present invention also provides a dealcohol condensation reaction of tetra-alkoxyorthosilicate with a mixture of (i) at least one aliphatic epoxy resin containing a hydroxy group and (ii) at least one aromatic epoxy resin containing a hydroxy group. And silicate-modified epoxy resins.

Examples of aliphatic epoxy resins containing hydroxyl groups include hydrogenated bisphenol A epoxy resins, and trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, butanediol diglycid Polyglycidyl ethers of polyhydric alcohols such as dill ether and hexanediol diglycidyl ether.

 Examples of aromatic epoxy resins containing hydroxyl groups include bisphenol epoxy resins and partially hydrolyzed novolac resins. Bisphenol epoxy resin can be obtained by reaction between bisphenol and haloepoxide, such as epichlorohydrin or β-methyl epichlorohydrin. Suitable bisphenols are the reactions between phenol or 2,6-dihalophenol and aldehydes or ketones such as formaldehyde, acetaldehyde, acetone, acetophenone, cyclohexanone, or benzophenone, oxidation of dihydroxyphenylsulfide by peracid Reaction and esterification of one or more hydroquinones.

The epoxy resin may partially react with the secondary amine before reacting with the tetra-alkoxyorthosilicate.

The epoxy equivalent of the epoxy resin containing a hydroxyl group is preferably about 180 to about 5,000 g / equivalent, and more preferably 180 to 1,000 g / equivalent. If the epoxy equivalent is less than 180 g / equivalent, the number of hydroxyl groups that can react with the tetra-alkoxyorthosilicate is too small to allow sufficient bonds to be formed between the epoxy resin and the tetra-alkoxyorthosilicate. When the epoxy equivalent exceeds 5,000 g / equivalent, the number of hydroxyl groups is too large to control the condensation reaction, and rapid gelation may occur.

Silicate-modified epoxy resins can be obtained by dealcohol condensation reactions of (partially hydrolyzed) tetra-alkoxyorthosilicates and epoxy resins containing hydroxyl groups. During the dealcohol condensation reaction, all or part of the hydroxyl groups of the epoxy resin are reacted with (partially hydrolyzed) tetra-alkoxyorthosilicates.

The weight ratio of epoxy resin: tetra-alkoxyorthosilicate is preferably in the range of 1:10 to 10: 1, more preferably 1: 1 to 5: 1.

Preferably, the ratio of the alkoxy group of the (partially hydrolyzed) tetra-alkoxyorthosilicate to the hydroxy group of the epoxy resin ranges from 2: 1 to 100: 1, more preferably 3: 1 to 50: 1, and most preferably 4: 1 to 12: 1. Stoichiometric ratios are undesirable because epoxy resins, on average, have one or more hydroxy groups per molecule, which can lead to products that form intractable gels. It is also possible to use excess hydroxyl groups, but the resulting product will have a high viscosity and will not exhibit rapid drying.

The dealcohol condensation reaction can be carried out by heating a mixture of the epoxy resin and (partially hydrolyzed) tetra-alkoxyorthosilicate in the presence of a catalyst. Tetra-alkoxyorthosilicates are very limited in their miscibility with organic polymers and phase separation occurs when mixed with organic polymers. This is in contrast to silanes having one or more Si—C bonds that are more miscible with the organic polymer and readily form a homogeneous mixture. Upon heating in the presence of a suitable catalyst, some reaction between the hydroxyl group of the epoxy resin and the orthosilicate occurs, which is confirmed by the change in the ¹ H NMR spectrum of the epoxy resin. As the reaction proceeds, the miscibility of the two components is enhanced to produce a homogeneous mixture of single phases.

The temperature of the reaction is preferably 50 ° C to 130 ° C, more preferably 70 ° C to 110 ° C. The reaction is carried out under substantially anhydrous conditions, preferably for about 1 to about 15 hours, in order to prevent the polymerization reaction of tetra-alkoxyorthosilicate.

Suitable catalysts for the dealcohol condensation reaction are commonly known catalysts which do not cause ring opening of the epoxy ring. Examples of such catalysts include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, and manganese; Same metals, their oxides, organic acid salts, halides, or alkoxides. Organotitanium and organotin compounds are preferred catalysts. More preferred are dibutyltin dilaurate and tetra-alkyl titanium compounds.

However, base catalysts such as amines should be avoided because they can react directly with epoxy groups on epoxy resins and can promote homopolymerisation of unwanted epoxy groups.

The resulting silicate-modified epoxy resin may contain some unreacted epoxy resin and / or unreacted tetra-alkoxyorthosilicate. Unreacted tetra-alkoxyorthosilicate can be converted to silica by hydrolysis and condensation reactions. In order to promote hydrolysis and condensation reactions, when silicate-modified epoxy resins are used, small amounts of water can be added thereto.

The coating composition according to the invention may take the form of a one-pack or two-pack composition.

The one-pack composition is moisture curable and requires the epoxy resin to react with the secondary amine before reacting with the (partially hydrolyzed) tetra-alkoxyorthosilicate. Therefore, the composition should be substantially free of moisture.

The two-pack composition will include the curing agent in a separate pack. Thus, Pack 1 will comprise a silicate-modified epoxy resin and Pack 2 will contain an epoxy reactive curing agent. Pack 1 preferably contains no base or other compounds capable of reacting with the epoxy functional groups of the silicate-modified epoxy resins. In particular, pack 1 preferably does not contain an amine. In addition, Pack 1 should be substantially moisture free.

“Substantially free of water” herein means that up to 1.0% by weight, more preferably up to 0.5% by weight and most preferably up to 0.1% by weight of water is contained.

The epoxy-reactive curing agent present in the two-pack coating composition can be any curing agent known as curing agent for epoxy resins. Examples of the phenol resin curing agent include polyamine curing agents, polythiol curing agents, polyanhydride curing agents, and polycarboxylic acid curing agents, and polyamine curing agents are preferred. Optionally, the curing agent may comprise an amino-functional organosiloxane capable of reacting with both epoxy and alkoxysilicate groups.

Examples of the phenol resin curing agent include phenol novolak resins, bisphenol novolak resins and poly p-vinylphenols.

Examples of the polyamine curing agent include diethylene triamine, triethylene tetramine, tetraethylene, pentamine, dicyanidiamide, polyamide-amine, polyamide resin, ketimine compound, isophorone diamine, m-xylene diamine , m-phenylene diamine, 1,3-bis (aminomethyl) cyclohexane, N-aminoethyl piperazine, 4,4'-diaminodiphenyl methane, 4,4'-diamino-3,3'- Diethyl-diphenyl methane, diaminodiphenyl sulfone and any adducts of these amines. Such adducts may be prepared by the reaction of an amine with a suitable reactive compound, such as an epoxy resin. This reduces the content of free amines in the curing agent, making it more suitable for use under conditions of low temperature and / or high humidity.

Examples of the polycarboxylic acid curing agent include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, hexachloroendomethylenetetrahydrophthalic anhydride and methyl-3,6-endomethylenetetrahydro Phthalic anhydride is mentioned.

The amount of curing agent present in the two-pack coating composition is preferably such that the equivalent ratio of functional groups having active hydrogen in the curing agent to the epoxy group of the silicate-modified epoxy resin is about 0.2 to 2.

In addition, the two-pack coating composition may include an accelerator to promote the curing reaction. Examples of suitable accelerators include 1,8-diaza-bicyclo [5.4.0] unde-7-cene, triethylene diamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol and tris (dimethylaminomethyl) phenol. Tertiary amines; Imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and 2-heptadecylimidazole; Organic phosphines such as tributyl phosphine, methyldiphenyl phosphine, triphenyl phosphine, diphenyl phosphine and phenyl phosphine; Nonyl phenol; Salicylic acid; Diazabicyclo octane; And calcium nitrate.

The accelerator is preferably used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the silicate-modified epoxy resin.

Accelerators may be present in Pack 1 (containing silicate-modified epoxy resins) and / or Pack 2 (containing hardeners).

The coating composition according to the present invention may contain a compound which acts as a catalyst for Si-O-Si condensation. In general, the coating can be cured under ambient conditions and humidity conditions that are surface tack-free coated after 2 to 20 minutes without such a catalyst, but it is desirable to provide more rapid curing by the catalyst.

An example of a catalyst for Si-O-Si condensation is an alkoxytitanium compound, for example a titanium chelate compound such as titanium bis (acetylacetonate) dialkoxide (e.g. titanium bis (acetylacetonate) diisopropoxide) ), Titanium bis (acetoacetate) dialkoxides (eg titanium bis (ethylacetoacetate) diisopropoxide) or alkanolamine titanates (eg titanium bis (triethanolamine) diisopropoxide), or tetra And alkoxytitanium compounds other than chelates such as (isopropyl) titanate or tetrabutyl titanate. The titanium compounds containing an alkoxy group bonded to titanium may not act solely as a catalyst, since the titanium alkoxide group is hydrolyzable and the catalyst is attached to the cured composition by Si-O-Ti bonds. Because it can. The presence of such titanium residues in the cured composition can be advantageous to provide even higher thermal stability. Titanium compounds can be used, for example, at 0.1 to 5% by weight of the binder. Corresponding alkoxide compounds of zirconium or aluminum are also useful as catalysts.

Another catalyst for Si-O-Si condensation is nitrates of polyvalent metal ions such as calcium nitrate, magnesium nitrate, aluminum nitrate, zinc nitrate, or strontium nitrate. If the composition also includes an organic amine, calcium nitrate is an effective catalyst for curing the silicates by Si-O-Si condensation. Calcium nitrate is preferably used in its tetrahydrate form, but may also be used in other hydrate forms. The level of calcium nitrate catalyst required is generally less than 3% by weight of the binder, for example 0.05 to 3% by weight. Coatings cured using calcium nitrate catalysts are particularly resistant to yellowing upon exposure to sunlight.

Another example of a suitable catalyst is an organotin compound, for example a dialkyltin dicarboxylate such as dibutyltin dilaurate or dibutyltin diacetate. Such organotin catalysts can be used, for example, at 0.05 to 3% by weight, based on the weight of the silicate-modified epoxy resin.

In the coating compositions of the present invention, other compounds effective as catalysts are organic salts such as carboxylates of bismuth, for example bismuth tris (neodecanoate). Organic salts and / or chelates of other metals such as zinc, aluminum, zirconium, tin, calcium, cobalt or strontium, for example zirconium acetylacetonate, zinc acetate, zinc acetylacetonate, zinc octoate, tin octoate ( stannous octoate, tin oxalate, calcium acetylacetonate, calcium acetate, calcium 2-ethylhexanoate, cobalt naphthenate, calcium dodecylbenzene sulfonate, or aluminum acetate may also be effective as a catalyst. .

The coating composition of the present invention may comprise one or more additional components. The solvent may be contained under the condition that the solid content is at least 70 vol%. One or more pigments, for example one or more reinforcing pigments such as titanium dioxide (white pigment), yellow or red iron oxide or phthalocyanine pigment and / or micaceous iron oxide or crystalline silica and / or Metal zinc, zinc phosphate, wollastonite or chromate, molybdate or phosphonate-like pigments and / or filter pigments such as barytes, talc or calcium carbonate Can be. The composition may also contain one or more thickeners, one or more plasticizers, pigment dispersants, stabilizers, mold releasing agents, surface modifiers, such as fine silica, bentonite clay, hydrogenated castor oil, or polyamide wax It may contain a surface modifier, a flame retardant, an antibacterial agent, an antifungal agent, a leveling agent, an antifoaming agent, and the like.

The coating compositions of the invention are generally cured at ambient or lower temperatures, such as -5 to 30 ° C, and are therefore suitable for application in large structures where heat-curing is impractical. The coating composition of the present invention may also be cured, if necessary, at elevated temperatures, for example from 30 or 50 ° C. to 100 or 130 ° C. Hydrolysis of silicon-bonded alkoxy groups depends on the presence of moisture. For most climates, atmospheric moisture is sufficient, but if the coating cures below ambient temperature, or at very low humidity (desert) locations, a controlled amount of moisture may need to be added to the coating. The water is preferably packaged separately from any compound or polymer containing silicon-bonded alkoxy groups.

The coating composition of the present invention can be used as a finish coating and / or a primer coating. Coating compositions containing a relatively high proportion of silicates have a high gloss that is excellently maintained even during weathering and UV exposure. It is particularly suitable for coating substrates that are exposed to weathering, for example for a long time, when exposed to weathering before recoating. The use of a solvent in the coating composition of the present invention is generally not necessary, but when the coating composition comprises an organic solvent (diluent) such as xylene, the highest level of gloss can be achieved. The coating composition may comprise an alcohol, such as ethanol or butanol, preferably packaged in pack 1, in order to prolong pot life and to control the initial cure rate. The finish coatings according to the invention are various primer coatings, for example inorganic zinc silicates or organic zinc-rich silicate primers and organic primers containing zinc metals, for example epoxy resins, anti-corrosion pigments, metal flakes, or barrier pigments. (barrier pigment) can be applied on. The coating composition according to the invention has a particularly good adhesion to inorganic zinc silicate coatings, without the need for an intermediate tie coat or a mist coat. The finish coating composition of the present invention, as well as a top coat, can act as a sealer and be applied directly onto an aluminum or zinc “metal spray” coating, or galvanized steel, stainless steel, aluminum or organic It can be applied directly on a plastic surface such as fiber reinforced polyester or on a polyester gel coat. Coating compositions can be used, for example, as finish coatings on buildings, steel structures, automobiles, aircraft and other vehicles, and general industrial machinery and devices. The finish coating may be colored or may be a transparent (non-colored) coat, especially when used in automobiles or yachts. The coating composition can be applied directly to carbon steel made as a primer / finish.

In addition, the coating compositions of the present invention can be used as protective primer coatings, especially on steel surfaces, for example bridges, pipelines, industrial facilities or buildings, oil and gas installations or ships. For this use, the coating composition is colored with an anticorrosive pigment. For example, it may be colored with zinc dust, and the coating composition according to the present invention has a similar anticorrosive performance to known zinc silicate coatings, but is not easily mud-cracked, for example as a finish coating according to the present invention. Can be easily overcoated. Primer coating compositions according to the present invention are either old and weathered steel or "ginger" (steel that has weathered and began to rust into small spots), hand-prepared weathered steel, and aged coating as a maintenance and repair coating on incomplete surfaces.

The coatings made from the compositions of the present invention not only have excellent resistance to UV weathering, but also have good stretch and good adhesion to most surfaces and have high heat resistance up to 150 ° C, usually up to 220 ° C.

It should also be noted that other moisture-reactive species, such as titanate, may be used instead of tetra-alkoxyorthosilicate for the modification of epoxy resins.

Example 1

In this example, silicate-modified epoxy resins were prepared by reacting a mixture of an aromatic bisphenol A-type epoxy resin containing a hydroxyl group with a partially condensed tetra-alkoxyorthosilicate in the presence of a catalyst.

Two aromatic bisphenol A epoxy resins containing partially condensed tetra-alkoxyorthosilicates (TES40) (119.88 g), tetra-n-butyl titanate (0.60 g) and hydroxy groups-DER 331 (376.74 g; solvent-free Liquid resin) and Epikote 836-X-80 (102.78 g; semi-solid resin containing 20 wt% xylene)-agitator, condenser, thermocouple and N ₂ Filled into a 700 ml reaction flask equipped with sparge. The reaction flask was purged with nitrogen for 15 minutes and the reaction was subsequently heated to 100 ° C. The reaction temperature was maintained at 100 ° C. for 3 hours, after which the reaction product was cooled to 40 ° C. and discharged.

The reactants were initially observed to be incompatible with each other. However, after 30 minutes at 100 ° C., the vessel contained a clear, uniform flowable liquid. According to ASTM standard D 4287-00, the viscosity of the resulting liquid, measured at 25 ° C. using a Sheen cone and plate viscometer, was 12 poise. The solids content, ie the non-volatile content, of the liquid was 90 to 92% by weight. The content of xylene in the liquid was about 3.5% by weight; The content of ethanol (formed during the reaction) was about 1.8% by weight. The remaining non-volatiles were the unreacted volatile components of the silicates.

The viscosity of the starting epoxy resin was 110-140 poise for DER 331 (according to their specifications) and 31-47 poise for Epicorte 836-X-80. This means that the silicate-modified epoxy resins have a significantly lower viscosity compared to the unmodified epoxy resins.

Examples 2-9

A silicate-modified epoxy resin was prepared in accordance with Example 1. Four different epoxy resins containing hydroxyl groups were used: two bisphenol A-type aromatic epoxy resins (DER 331 and DER 660-X-80) and two aliphatic epoxy resins (hexanediol diglycidyl ether (HDDGE) ) And hydrogenated bisphenol A diglycidyl ether (Eponex 1510)). Such compositions are described in more detail in Table 1. The table below also shows the viscosity of the resulting resin composition.

[Table 1]

It is clear from the above examples that it is possible to produce epoxy silicates with extremely low viscosities without the addition of solvents. When using an aliphatic epoxy resin or a mixture of aliphatic and aromatic epoxy resins, the best results can be obtained.

Example 10-19

The silicate-modified epoxy resins of Examples 3-9 and some additional epoxy resins (epoxy resins prepared according to the method of Example 1, described in Table 2) were mixed with cycloaliphatic amine curing agents. In all the examples, the same curing agent was used, and the curing agent was prepared such that the ratio of epoxy group: active hydrogen was 1: 1. A tertiary amine catalyst, DBU (1,8-diaza-bicyclo [5.4.0] und-7-cene), was added at a constant molar ratio. The resulting coating composition was applied onto the surface. The coating composition cured rapidly at low temperatures. The VOCs of all the coating compositions were lower than 250 g / l and the solids content was higher than 70 volume percent.

Mix viscosity and curing time at 10 ° C. are listed in Table 2. At 25 ° C., the mixing viscosity was recorded as poise. Cure time means the time it takes to achieve step III, as described in ASTM D 5895-03, and is synonymous with “Dry Hard Time”.

[Table 2]

Example 20

The pot life of the coating composition of Example 14 was determined by measuring the increase in viscosity of the composition over time, according to ISO 9514: 1992. Pot life is increased when the viscosity of the mixture is above that which allows for spray application. According to ASTM standard D 4287-00, measurements were made at 25 ° C. using a sheen cone and plate viscometer.

The pot life of the coating composition was 1.5-2 hours.

Example 21

(i) the epoxy resin was agitated, condenser, thermocouple and N ₂ Fill a 700 ml reaction flask with sparge, (ii) raise the temperature to 100 ° C., (iii) add dibutylamine over 3 hours, and (iv) bring the reaction product to 40 ° C. Following a cooling step, a single pack is prepared by first pre-reacting an aromatic bisphenol A-type epoxy resin-DER 331, (374.0 g)-containing a hydroxy group, with a stoichiometric amount of dibutylamine (258.0 g) first Silicate-modified epoxy resins were prepared.

The resulting DER331-dibutylamine adduct (210.7 g), partially condensed tetra-ethoxyorthosilicate-TES40 (217.0 g)-and tetra-n-butyl titanate catalyst (0.40 g) were added to the stirrer, condenser, Thermocouple and N ₂ Filled into a 700 ml reaction flask equipped with sparge. The mixture was heated to 100 ° C., maintained at this temperature for 3 hours and then cooled to 40 ° C. before the reaction product was discharged.

The reactants were initially incompatible with each other. However, after 30 minutes at 100 ° C., the container contained a clear liquid. The resulting material was a clear, uniform flowable liquid with a viscosity of 6.6 poise at 25 ° C.

A sample of the resulting material is cast on a glass panel, without additional curing agent or catalyst, and its curing time (step III), which has the same meaning as "Dry Hard Time," ASTM D 5895-03 The drying time was recorded as 2 hours 45 minutes at 10 ° C.

Claims (10)

A coating composition comprising a reaction product of tetra-alkoxyorthosilicate or an epoxy resin containing hydroxy groups with a partially condensed oligomer thereof and having a solids content of at least 70% by volume and a volatile organic content (VOC) of at most 250 g / l . The method of claim 1,
The coating composition containing the said hydroxyl group is an aliphatic epoxy resin. The method of claim 1,
Wherein said epoxy resin containing a hydroxyl group is a mixture of at least one aliphatic epoxy resin containing a hydroxyl group and at least one aromatic epoxy resin containing a hydroxyl group. A silicate-modified epoxy resin obtainable by dealcoholisation condensation of a tetra-alkoxyorthosilicate or an aliphatic epoxy resin containing a hydroxyl group with an oligomer thereof partially condensed. Silicate-modified epoxy obtainable by dealcohol condensation reaction of tetra-alkoxysilicate or its partially condensed oligomer with at least one aliphatic epoxy resin containing hydroxy groups and at least one aromatic epoxy resin mixture containing hydroxy groups Suzy. A method for preparing the silicate-modified epoxy resin of claim 4 or 5, wherein
A mixture of tetra-alkoxyorthosilicate or its partially condensed oligomer with an aliphatic epoxy resin containing a hydroxy group; or
Tetra-alkoxyorthosilicate or a mixture of oligomers thereof partially condensed with one or more aliphatic epoxy resins containing hydroxy groups and one or more aromatic epoxy resins containing hydroxy groups
To produce the silicate-modified epoxy resin by heating in the presence of a catalyst. Use of the silicate-modified epoxy resin of claim 4 or 5 for coating a substrate. As a method of coating a substrate,
(i) applying the coating composition of any one of claims 1 to 3 to the substrate, and
(ii) curing the applied coating composition
≪ / RTI > 9. The method of claim 8,
The coating method wherein the curing is performed at a temperature in the range of -5 to 30 ° C. A coated substrate obtainable by the method of claim 8 or 9.